EP4256011B1 - Zusammensetzung - Google Patents

Zusammensetzung Download PDF

Info

Publication number
EP4256011B1
EP4256011B1 EP21814812.0A EP21814812A EP4256011B1 EP 4256011 B1 EP4256011 B1 EP 4256011B1 EP 21814812 A EP21814812 A EP 21814812A EP 4256011 B1 EP4256011 B1 EP 4256011B1
Authority
EP
European Patent Office
Prior art keywords
alcohol ethoxylate
composition
composition according
alkyl
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP21814812.0A
Other languages
English (en)
French (fr)
Other versions
EP4256011A1 (de
EP4256011C0 (de
Inventor
Stephen Norman Batchelor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4256011A1 publication Critical patent/EP4256011A1/de
Application granted granted Critical
Publication of EP4256011B1 publication Critical patent/EP4256011B1/de
Publication of EP4256011C0 publication Critical patent/EP4256011C0/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

  • the present invention relates to an improved laundry liquid composition.
  • Aqueous liquid laundry detergent compositions comprising C12-14 alcohol ethoxylates are ubiquitous.
  • the alkyl chains of the surfactants are made from petrochemicals or oil derived from palm kernel oil.
  • the dose of aqueous laundry liquid composition required for a wash are typically dispensed from approximately 0.5 to 5 litre bottles or cartons directly into the wash liquor or washing machine.
  • a liquid laundry detergent composition comprising C16 and C18 alcohol ethoxylate surfactant wherein the C18 alcohol ethoxylate comprises monounsaturated C18, wherein the proportion of monounsaturated C18 constitutes at least 50% wt. of the total C16 and C18 alcohol ethoxylate surfactant and wherein the C16 alcohol ethoxylate comprises at least 4% of the total C16 and C18 alcohol ethoxylate surfactant and wherein the C16 and 18 alcohol ethoxylate has an average of from 8 to 20 EO groups.
  • the C16 and C18 alcohol ethoxylate surfactant is present at from 1 to 30% wt., more preferably from 2 to 10% wt. of the composition, most preferably 5 to 10 wt.%.
  • the composition comprises C16/18 alcohol ethoxylate of the formula: R 1 -O-(CH 2 CH 2 O) q -H where R 1 is selected from saturated, monounsaturated and polyunsaturated linear C16 and C18 alkyl chains and where q is from 4 to 20, preferably 5 to 14, more preferably 8 to 12.
  • the mono-unsaturation is preferably in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end.
  • the double bond may be in a cis or trans configuration (oleyl or elaidyl), preferably cis.
  • R1 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, the saturated C16 alcohol ethoxylate is at least 90% wt. of the C16 linear alcohol ethoxylate. As regards the C18 alcohol ethoxylate content, it is preferred that the predominant C18 moiety is C18:1, more preferably C18:1( ⁇ 9).
  • the proportion of monounsaturated C18 alcohol ethoxylate constitutes at least 50% wt. of the total C16 and C18 alcohol ethoxylate surfactant. Preferably, the proportion of monounsaturated C18 constitutes at least 60% wt., most preferably at least 75 of the total C16 and C18 alcohol ethoxylate surfactant.
  • the C16 alcohol ethoxylate surfactant comprises at least 2% wt. and more preferably, from 4% of the total C16 and C18 alcohol ethoxylate surfactant.
  • the saturated C18 alcohol ethoxylate surfactant comprises up to 20% wt. and more preferably, up to 11% of the total C16 and C18 alcohol ethoxylate surfactant.
  • the saturated C18 content is at least 2% wt. of the total C16 and C18 alcohol ethoxylate content.
  • Alcohol ethoxylates are discussed in the N on-ionic Surfactants: Organic Chemistry edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series published by CRC press . Alcohol ethoxylates are commonly referred to as alkyl ethoxylates.
  • the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1, more preferably from 2 to 100, most preferably 3 to 30.
  • 'C18 alcohol ethoxylate' is the sum of all the C18 fractions in the alcohol ethoxylate and 'C16 alcohol ethoxylate' is the sum of all the C16 fractions in the alcohol ethoxylate.
  • the total C18:1 alcohol ethoxylate content is at least 70% wt. of the total C18 alcohol ethoxylate content.
  • the total C18:0 alcohol ethoxylate content is less than 20% of the total C16 and C18 alcohol ethoxylate content.
  • the C18 alcohol ethoxylate to C16 alcohol ethoxylate content is less than 3.5, more preferably less than 3.
  • the C16 alcohol ethoxylate content is at least 25% of the total C16 and C18 alcohol ethoxylate content combined.
  • Linear saturated or mono-unsaturated C20 and C22 alcohol ethoxylate may also be present.
  • the weight fraction of sum of 'C18 alcohol ethoxylate' / 'C20 and C22 alcohol ethoxylate' is greater than 10.
  • the C16/18 alcohol ethoxylate contains less than 15wt%, more preferably less than 8 wt%, most preferably less than 5 wt% of the alcohol ethoxylate polyunsaturated alcohol ethoxylates.
  • a polyunsaturated alcohol ethoxylate contains a hydrocarbon chains with two or more double bonds.
  • C16/18 alcohol ethoxylates may be synthesised by ethoxylation of an alkyl alcohol, via the reaction:.
  • the alkyl alcohol may be produced by transesterification of the triglyceride to a methyl ester, followed by distillation and hydrogenation to the alcohol. The process is discussed in Journal of the American Oil Chemists' Society. 61 (2): 343-348 by Kreutzer, U. R.
  • Preferred alkyl alcohol for the reaction is oleyl alcohol with in an iodine value of 60 to 80, preferably 70 to 75, such alcohol are available from BASF, Cognis, Ecogreen.
  • the ethoxylation reactions are base catalysed using NaOH, KOH, or NaOCH 3 .
  • catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCH 3 .
  • these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in WO2007/147866 . Lanthanides may also be used.
  • Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.
  • q 10
  • greater than 70 wt.% of the alcohol ethoxylate should consist of ethoxylate with 5, 6, 7, 8, 9 10, 11, 12, 13, 14 and 15 ethoxylate groups.
  • the composition comprises a non-ionic surfactant in addition to the surfactants described above.
  • the composition comprises from 5 to 20% wt. non-ionic surfactant based on the total weight of composition including the C16/18 non-ionic surfactants and any other nonionic surfactants, for example, polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide.
  • Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate.
  • the polyoxyalkylene compounds can have a variety of block and heteric (random) structures.
  • they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates.
  • the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides.
  • Examples of such materials include C 8 to C 22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as C 8 to C 18 primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
  • a preferred class of additional nonionic surfactant for use in the invention includes aliphatic C 12 to C 15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.
  • the alcohol ethoxylate comprising a C16 and/or C18 alkyl chain comprises less than 30% wt., more preferably less than 20%, especially preferably less than 10% wt. and most preferably less than 5% wt. alcohol ethoxylate comprising less than 6 EO groups.
  • the alcohol ethoxylate may be provided in a single raw material component or by way of a mixture of components.
  • the composition comprises a mixture of the C16/18 sourced material for the alcohol ethoxylate as well as the more traditional C12 alkyl chain length materials it is preferred that the total C16/18 alcohol ethoxylate content should comprise at least 10% wt. total alcohol ethoxylate, more preferably at least 50%, even more preferably at least 70%, especially preferably at least 90% and most preferably at least 95% of the alcohol ethoxylate in the composition.
  • the alcohol ethoxylate comprise at least 60%, more preferably at least 80%, especially preferably at least 90% and most preferably at least 95% of the total non-ionic surfactant content.
  • a further class of non-ionic surfactants include the alkyl poly glycosides.
  • Rhamnolipids are another preferred additional surfactant.
  • the alkyl chain of C16/18 surfactant is preferably obtained from a renewable source, preferably from a triglyceride.
  • a renewable source is one where the material is produced by natural ecological cycle of a living species, preferably by a plant, algae, fungi, yeast or bacteria, more preferably plants, algae or yeasts.
  • Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees.
  • the oil from trees is called tall oil.
  • Palm and Rapeseed oils are the source.
  • Algal oils are discussed in Energy Environ. Sci., 2019,12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents by Masri M.A. et al.
  • Non edible plant oils may be used and are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L.(castor), Simmondsia chinensis (Jojoba), Eruca sativa.
  • the weight ratio of non-ionic to anionic surfactant is from 2:1 to 1:6.
  • the weight ratio of non-ionic surfactant to alkyl ether sulphate surfactant is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably 0.9 to 1.1.
  • the weight ratio of non-ionic surfactant to linear alkyl benzene sulphonate, where present, is from 0.1 to 2, preferably 0.3 to 1, most preferably 0.45 to 0.85.
  • the composition preferably comprises an anionic surfactant.
  • anionic surfactants for use in the invention are typically salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl” being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, C12-C14 alkyl ether sulfates, alkaryl sulfonates, alphaolefin sulfonates and mixtures thereof.
  • the alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated.
  • the C12-C14 alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule.
  • Alkyl ether sulfates are also called alcohol ether sulfates.
  • Anionic surfactants are described in anionic surfactants, volume 56 of the Surfactant Science Seried (H.W. Stache editor) Dekker 1995 .
  • C12-C14 alkyl ether sulfates having a straight or branched chain alkyl group having 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule.
  • a preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.
  • the C12-C14 alkyl ether sulphate may be provided in a single raw material component or by way of a mixture of components.
  • the counterion for any of the anionic surfactants used in the compositions described herein is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as ammonium, monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed.
  • compositions according to the invention may preferably include alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms.
  • LAS linear alkylbenzene sulfonates
  • Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the "para" position and attached to a linear alkyl chain at any position except the terminal carbons.
  • the linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12.
  • Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer.
  • LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.
  • alkyl sulfate surfactant may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.
  • the composition comprises C16 and C18 ether sulfate of the formula: R 2 -O-(CH 2 CH 2 O) p SO 3 H
  • R 2 is selected from saturated, monounsaturated and polyunsaturated linear C16 and C18 alkyl chains and where p is from 3 to 20, preferably 4 to 12, more preferably 5 to 10.
  • the mono-unsaturation is preferably in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end.
  • the double bond may be in a cis or trans configuration (oleyl or elaidyl), but is preferably cis.
  • R2 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, the saturated C16 is at least 90% wt. of the C16 content linear alkyl. As regards the C18 content, it is preferred that the predominant C18 moiety is C18:1, more preferably C18:1( ⁇ 9). Preferably, the proportion of monounsaturated C18 constitutes at least 50% wt. of the total C16 and C18 alkyl ether sulphate surfactant.
  • the proportion of monounsaturated C18 constitutes at least 60% wt., most preferably at least 75 of the total C16 and C18 alkyl ether sulphate surfactant.
  • the C16 alkyl ether sulphate surfactant comprises at least 2% wt. and more preferably, from 4% of the total C16 and C18 alkyl ether sulphate surfactant.
  • the saturated C18 alkyl ether sulphate surfactant comprises up to 20% wt. and more preferably, up to11% of the total C16 and C18 alkyl ether sulphate surfactant.
  • the saturated C18 content is at least 2% wt. of the total C16 and C18 alkyl ether sulphate content.
  • the composition comprises a mixture of the C16/18 sourced material for the alkyl ether sulphate as well as the more traditional C12 alkyl chain length materials it is preferred that the total C16/18 alkyl ether sulphate content should comprise at least 10% wt. of the total alkyl ether sulphate, more preferably at least 50%, even more preferably at least 70%, especially preferably at least 90% and most preferably at least 95% of alkyl ether sulphate in the composition.
  • Ether sulfates are discussed in the Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series published by CRC press .
  • Linear saturated or mono-unsaturated C20 and C22 ether sulfate may also be present.
  • the weight fraction of sum of 'C18 ether sulfate' / 'C20 and C22 ether sulfate' is greater than 10.
  • the C16 and C18 ether sulfate contains less than 15 wt.%, more preferably less than 8 wt.%, most preferably less than 4wt% and most preferably less than 2% wt. of the ether sulfate polyunsaturated ether sulfate.
  • a polyunsaturated ether sulfate contains a hydrocarbon chains with two or more double bonds.
  • Ether sulfate may be synthesised by the sulphonation of the corresponding alcohol ethoxylate.
  • the alcohol ethoxylate may be produced by ethoxylation of an alkyl alcohol.
  • the alkyl alcohol used to produced the alcohol ethoxylate may be produced by transesterification of the triglyceride to a methyl ester, followed by distillation and hydrogenation to the alcohol. The process is discussed in Journal of the American Oil Chemists' Society. 61 (2): 343-348 by Kreutzer, U. R.
  • Preferred alkyl alcohol for the reaction is oleyl alcohol with an iodine value of 60 to 80, preferably 70 to 75, such alcohol are available from BASF, Cognis, Ecogreen.
  • the degree of polyunsaturation in the surfactant may be controlled by hydrogenation of the triglyceride as described in: A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017 ). Distillation and other purification techniques may be used. Ethoxylation reactions are described in Non-ionic Surfactant Organic Chemistry (N. M. van Os ed), Surfactant Science Series Volume 72, CRC Press .
  • the ethoxylation reactions are base catalysed using NaOH, KOH, or NaOCH 3 .
  • catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCH 3 .
  • these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in WO2007/147866 . Lanthanides may also be used.
  • Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.
  • the ether sulfate weight is calculated as the protonated form: R 2 -O-(CH 2 CH 2 O) p SO 3 H.
  • R 2 -O-(CH 2 CH 2 O) p SO 3 H In the formulation it will be present as the ionic form R 2 -O-(CH 2 CH 2 O) p SO 3 - with a corresponding counter ion, preferred counter ions are group I and II metals, amines, most preferably sodium.
  • the composition comprises both alcohol ethoxylate and alkyl ether sulphate.
  • the alcohol ethoxylate comprises C18 alkyl chains as described above and the alkyl ether sulphate comprises sodium lauryl ether (1-3EO) sulphate and/or sodium C18 ether sulphate as described above.
  • linear alkyl benzene sulphonate surfactant is present at from 1 to 20% wt., more preferably from 2 to 15% wt. of the composition, most preferably 8 to 12 wt.%.
  • Weight ratios are calculated for the protonated form of the surfactant.
  • laundry detergent in the context of this invention denotes formulated compositions intended for and capable of wetting and cleaning domestic laundry such as clothing, linens and other household textiles.
  • the object of the invention is to provide a composition which on dilution is capable of forming a liquid laundry detergent composition and in the manner now described.
  • Textiles can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.
  • liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.
  • liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.
  • liquid in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above. Accordingly, the term “liquid” may encompass emulsions, suspensions, but not compositions having flowable yet stiffer consistency, known as gels or pastes.
  • the viscosity of the composition is preferably from 100 to about 1,000 mPa.s at 25°C at a shear rate of 21 sec -1 . This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle.
  • Pourable liquid detergent compositions preferably have a viscosity of from 200 to 500 mPa.s, preferably from 200 to 300 mPa.s.
  • the composition of the invention comprises from 50% water, more preferably from 60% wt. water, especially preferably from 70% wt water and most preferably from 75% water.
  • the water used has a french hardness of less than 5 degrees french hard, most preferably it is demineralised.
  • the water is treated with a disinfectant, preferably selected from a chlorine based disinfectant, ozone or UV treatment, to sterilized the water.
  • the composition comprises less than 0.6% wt. EDTA.
  • a composition according to the invention may suitably have an aqueous continuous phase.
  • aqueous continuous phase is meant a continuous phase which has water as its basis.
  • the formulation has a pH of 5 to 10, more preferably 6 to 8, most preferably 6.1 to 7.0.
  • a composition of the invention suitably comprises from 5 to 60% and preferably from 10 to 40% (by weight based on the total weight of the composition) of one or more detersive surfactants.
  • detersive surfactant in the context of this invention denotes a surfactant which provides a detersive (i.e. cleaning) effect to laundry treated as part of a domestic laundering process.
  • the selection and amount of surfactant is such that the composition and the diluted mixture are isotropic in nature.
  • composition may also comprise an anti-foam.
  • Anti-foam materials are well known in the art and include silicones and fatty acid.
  • fatty acid soap is present at from 0 to 3.0% wt. of the composition, more preferably from 0 to 0.5% wt. and most preferably zero.
  • Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid
  • fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids.
  • Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).
  • the fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • fatty acids and/or their salts are not included in the level of surfactant or in the level of builder.
  • Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil.
  • Suitable soil release polymers for use in the invention include alkoxylated polyethyleneimines.
  • Polyethyleneimines are materials composed of ethylene imine units -CH 2 CH 2 NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • Preferred alkoxylated polyethyleneimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M w ).
  • the polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer.
  • the alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both.
  • a nitrogen atom is alkoxylated
  • a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification.
  • a preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
  • a composition of the invention will preferably comprise from 0.025 to 8% wt. of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines which are described above.
  • Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing.
  • the adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.
  • SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped.
  • the SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity.
  • the weight average molecular weight (M w ) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
  • SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol).
  • the copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units.
  • oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol ("EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
  • DMT dimethyl terephthalate
  • PG propylene glyco
  • cellulosic derivatives such as hydroxyether cellulosic polymers, C 1 -C 4 alkylcelluloses and C 4 hydroxyalkyl celluloses
  • Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (I):
  • n, n and a are not necessarily whole numbers for the polymer in bulk.
  • the overall level of SRP when included, may range from 0.1 to 10%, depending on the level of polymer intended for use in the final diluted composition and which is desirably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the diluted composition).
  • soil release polymers are described in greater detail in U. S. Patent Nos. 5,574,179 ; 4,956,447 ; 4,861,512 ; 4,702,857 , WO 2007/079850 and WO2016/005271 . If employed, soil release polymers will typically be incorporated into the liquid laundry detergent compositions herein in concentrations ranging from 0.01 percent to 10 percent, more preferably from 0.1 percent to 5 percent, by weight of the composition.
  • a composition of the invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers.
  • non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers.
  • Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (M w ) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene,
  • Non-aqueous carriers when included, may be present in an amount ranging from 0.1 to 20%, preferably from 2 to 15%, and more preferably from 10 to 14% (by weight based on the total weight of the composition).
  • the level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such compositions.
  • the preferred hydrotropes are monopropylene glycol and glycerol.
  • the composition comprises less than 3% wt. alkanol comprising 1 to 3 carbons. More preferably the composition comprises less than 3% wt. ethanol.
  • a composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above.
  • cosurfactants such as amphoteric (zwitterionic) and/or cationic surfactants
  • Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof.
  • Cationic surfactant when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
  • amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms preferably selected from C12, C14, C16 ,C18 and C18:1, the term "alkyl” being used to include the alkyl portion of higher acyl radicals.
  • Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • DEQUEST TM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
  • organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALAN TM .
  • the organic builder materials may comprise from about 0.5 percent to 20 wt percent, preferably from 1 wt percent to 10 wt percent, of the composition.
  • the preferred builder level is less than 10 wt percent and preferably less than 5 wt percent of the composition.
  • the liquid laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 2 wt.%, preferably less than 1% wt. of phosphate. Most preferably the laundry detergent formulation is not built i.e. contain less than 1 wt.% of builder.
  • a preferred sequestrant is HEDP (1 -Hydroxyethylidene -1,1,-diphosphonic acid), for example sold as Dequest 2010. Also suitable but less preferred as it gives inferior cleaning results is Dequest(R) 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
  • a composition of the invention may comprise one or more polymeric thickeners.
  • Suitable polymeric thickeners for use in the invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers.
  • HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer.
  • associative monomer in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section.
  • a preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section.
  • Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from linear or branched C 8 -C 40 alkyl (preferably linear C 12 -C 22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one further monomer selected from C 1 -C 4 alkyl (meth) acrylates, polyacidic vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof.
  • the polyethoxylated portion of the associative monomer (i) generally comprises about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.
  • a composition of the invention will preferably comprise from 0.01 to 5% wt. of the composition but depending on the amount intended for use in the final diluted product and which is desirably from 0.1 to 3% wt. by weight based on the total weight of the diluted composition.
  • fluorescer in the compositions.
  • these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt % the composition.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
  • the fluoescer is a Di-styryl biphenyl compound, preferably Sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzenesulfonate ( CAS-No 27344-41-8 ).
  • Shading dye can be used to improve the performance of the compositions.
  • Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
  • a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
  • Shading dyes are well known in the art of laundry liquid formulation.
  • Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates.
  • Disperse Violet 28 Acid Violet 50
  • Alkoxylated thiophene dyes are discussed in WO2013/142495 and WO2008/087497 .
  • the shading dye is preferably present is present in the composition in range from 0.0001 to 0.1wt %. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class.
  • compositions of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the composition.
  • external structurants include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre.
  • the presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid.
  • a composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof.
  • the enzymes are preferably present with corresponding enzyme stabilizers.
  • composition preferably comprises a preservative.
  • the composition comprises a preservative to inhibit microbial growth.
  • preservatives may optionally be included in various embodiments as a way to further boost microbial protection for gross bacteria, virus and/or fungi contamination introduced e.g., by a consumer, through a contaminated ingredient, contaminated storage container, equipment, processing step or other source. Any conventional preservative known in the art may be used.
  • Some illustrative preservatives include: potassium sorbate, sodium benzoate, benzoic acid, phenoxyethanol, benzyl alcohol, dehydoxyacetic acid, sodium borate, boric acid, usinic acid, phenols, quaternary ammonia compounds, glycols, isothiazolinones (methyl, benzyl, chloro), DMDM hydantoin, hexidine, ethanol, IPBC, polyaminopropyl biguanide, phenylphenol, imidazolidinyl urea, parabens, formaldehyde, salicylic acid or salts, caprylyl glycol, D-glucono-1,5 lactone, sodium erythorbate, sodium hydroxymethylglycinate, peroxides, sodium sulphite, bisulphite, glucose oxidase, lacto peroxidase, and other preservatives compatible with the cleaning ingredients.
  • preservatives that do not compete with the cleaning ingredients and do not have reported health or environmental issues.
  • Some of the more preferred preservatives are: phenoxyethanol, benzoic acid/potassium sorbate, enzymes, borates, isothiazolinones such as MIT, BIT and CIT, and the natural solutions above.
  • the preservative is present in an amount less than about 5 wt. percent based on the total weight of the cleaning composition.
  • the preservative is present in an amount from about 0.01 to about 2 wt. percent.
  • the fragrant agent is present in an amount from about 0.01 to about 1 wt. percent.
  • the composition comprises BIT and/or MIT at a combined level of not more than 550 ppm and more preferably at from 300 to 450 ppm.
  • the level of MIT does not exceed 95 ppm.
  • the level of BIT does not exceed 450 ppm.
  • the composition comprises benzoate salt as preservative.
  • the benzoate salt is present at from 0.01 to 3% wt., more preferably from 0.1 to 2% wt. and most preferably from 0.5 to 1.5% wt. of the composition.
  • Fragrances are well known in the art and may be incorporated into compositions described herein.
  • microencapsulation may be defined as the process of surrounding or enveloping one substance within another substance on a very small scale, yielding capsules ranging from less than one micron to several hundred microns in size.
  • the material that is encapsulated may be called the core, the active ingredient or agent, fill, payload, nucleus, or internal phase.
  • the material encapsulating the core may be referred to as the coating, membrane, shell, or wall material.
  • Microcapsules typically have at least one generally spherical continuous shell surrounding the core.
  • the shell may contain pores, vacancies or interstitial openings depending on the materials and encapsulation techniques employed.
  • Multiple shells may be made of the same or different encapsulating materials, and may be arranged in strata of varying thicknesses around the core.
  • the microcapsules may be asymmetrically and variably shaped with a quantity of smaller droplets of core material embedded throughout the microcapsule.
  • the shell may have a barrier function protecting the core material from the environment external to the microcapsule, but it may also act as a means of modulating the release of core materials such as fragrance.
  • a shell may be water soluble or water swellable and fragrance release may be actuated in response to exposure of the microcapsules to a moist environment.
  • a microcapsule might release fragrance in response to elevated temperatures.
  • Microcapsules may also release fragrance in response to shear forces applied to the surface of the microcapsules.
  • a preferred type of polymeric microparticle suitable for use in the invention is a polymeric core-shell microcapsule in which at least one generally spherical continuous shell of polymeric material surrounds a core containing the fragrance formulation (f2).
  • the shell will typically comprise at most 20% by weight based on the total weight of the microcapsule.
  • the fragrance formulation (f2) will typically comprise from about 10 to about 60% and preferably from about 20 to about 40% by weight based on the total weight of the microcapsule.
  • the amount of fragrance (f2) may be measured by taking a slurry of the microcapsules, extracting into ethanol and measuring by liquid chromatography.
  • Polymeric core-shell microcapsules for use in the invention may be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization, and polycondensation.
  • Coacervation typically involves encapsulation of a generally water-insoluble core material by the precipitation of colloidal material(s) onto the surface of droplets of the material.
  • Coacervation may be simple e.g. using one colloid such as gelatin, or complex where two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled conditions of pH, temperature and concentration.
  • Interfacial polymerisation typically proceeds with the formation of a fine dispersion of oil droplets (the oil droplets containing the core material) in an aqueous continuous phase.
  • the dispersed droplets form the core of the future microcapsule and the dimensions of the dispersed droplets directly determine the size of the subsequent microcapsules.
  • Microcapsule shell-forming materials are contained in both the dispersed phase (oil droplets) and the aqueous continuous phase and they react together at the phase interface to build a polymeric wall around the oil droplets thereby to encapsulate the droplets and form core-shell microcapsules.
  • An example of a core-shell microcapsule produced by this method is a polyurea microcapsule with a shell formed by reaction of diisocyanates or polyisocyanates with diamines or polyamines.
  • Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of precondensate of polymeric materials under appropriate conditions of agitation to produce capsules of a desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in the condensate separating from solution and surrounding the dispersed core material to produce a coherent film and the desired microcapsules.
  • An example of a core-shell microcapsule produced by this method is an aminoplast microcapsule with a shell formed from the polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde.
  • Suitable cross-linking agents e.g. toluene diisocyanate, divinyl benzene, butanediol diacrylate
  • secondary wall polymers may also be used as appropriate, e.g. anhydrides and their derivatives, particularly polymers and co-polymers of maleic anhydride.
  • One example of a preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably such an aminoplast shell is formed from the polycondensation product of melamine with formaldehyde.
  • Polymeric microparticles suitable for use in the invention will generally have an average particle size between 100 nanometers and 50 microns. Particles larger than this are entering the visible range.
  • particles in the sub-micron range include latexes and mini-emulsions with a typical size range of 100 to 600 nanometers.
  • the preferred particle size range is in the micron range.
  • particles in the micron range include polymeric core-shell microcapsules (such as those further described above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns.
  • the average particle size can be determined by light scattering using a Malvern Mastersizer with the average particle size being taken as the median particle size D (0.5) value.
  • the particle size distribution can be narrow, broad or multimodal. If necessary, the microcapsules as initially produced may be filtered or screened to produce a product of greater size uniformity.
  • Polymeric microparticles suitable for use in the invention may be provided with a deposition aid at the outer surface of the microparticle.
  • Deposition aids serve to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate.
  • Desired substrates include cellulosics (including cotton) and polyesters (including those employed in the manufacture of polyester fabrics).
  • the deposition aid may suitably be provided at the outer surface of the microparticle by means of covalent bonding, entanglement or strong adsorption.
  • Examples include polymeric core-shell microcapsules (such as those further described above) in which a deposition aid is attached to the outside of the shell, preferably by means of covalent bonding. While it is preferred that the deposition aid is attached directly to the outside of the shell, it may also be attached via a linking species.
  • Deposition aids for use in the invention may suitably be selected from polysaccharides having an affinity for cellulose.
  • polysaccharides may be naturally occurring or synthetic and may have an intrinsic affinity for cellulose or may have been derivatised or otherwise modified to have an affinity for cellulose.
  • Suitable polysaccharides have a 1-4 linked ⁇ glycan (generalised sugar) backbone structure with at least 4, and preferably at least 10 backbone residues which are ⁇ 1-4 linked, such as a glucan backbone (consisting of ⁇ 1-4 linked glucose residues), a mannan backbone (consisting of ⁇ 1-4 linked mannose residues) or a xylan backbone (consisting of ⁇ 1-4 linked xylose residues).
  • ⁇ 1-4 linked polysaccharides examples include xyloglucans, glucomannans, mannans, galactomannans, ⁇ (1-3),(1-4) glucan and the xylan family incorporating glucurono-, arabino- and glucuronoarabinoxylans.
  • Preferred ⁇ 1-4 linked polysaccharides for use in the invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a ⁇ 1-4 linked glucan backbone with side chains of ⁇ -D xylopyranose and ⁇ -D-galactopyranosyl-(1-2)- ⁇ -D-xylo-pyranose, both 1-6 linked to the backbone); and galactomannans of plant origin such as loc ust bean gum (LBG) (which has a mannan backbone of ⁇ 1-4 linked mannose residues, with single unit galactose side chains linked ⁇ 1-6 to the backbone).
  • TXG pea xyloglucan and tamarind seed xyloglucan
  • LBG loc ust bean gum
  • polysaccharides which may gain an affinity for cellulose upon hydrolysis, such as cellulose mono-acetate; or modified polysaccharides with an affinity for cellulose such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar, hydroxyethyl ethylcellulose and methylcellulose.
  • Deposition aids for use in the invention may also be selected from phthalate containing polymers having an affinity for polyester.
  • phthalate containing polymers may have one or more nonionic hydrophilic segments comprising oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments comprising terephthalate groups.
  • the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300.
  • a suitable example of a phthalate containing polymer of this type is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.
  • Deposition aids for use in the invention will generally have a weight average molecular weight (M w ) in the range of from about 5 kDa to about 500 kDa, preferably from about 10 kDa to about 500 kDa and more preferably from about 20 kDa to about 300 kDa.
  • M w weight average molecular weight
  • One example of a particularly preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with a shell formed by the polycondensation of melamine with formaldehyde; surrounding a core containing the fragrance formulation (f2); in which a deposition aid is attached to the outside of the shell by means of covalent bonding.
  • the preferred deposition aid is selected from ⁇ 1-4 linked polysaccharides, and in particular the xyloglucans of plant origin, as are further described above.
  • the present inventors have surprisingly observed that it is possible to reduce the total level of fragrance included in the composition of the invention without sacrificing the overall fragrance experience delivered to the consumer at key stages in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.
  • the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the composition of the invention suitably ranges from 0.5 to 1.4%, preferably from 0.5 to 1.2%, more preferably from 0.5 to 1% and most preferably from 0.6 to 0.9% (by weight based on the total weight of the composition).
  • the weight ratio of fragrance formulation (f1) to fragrance formulation (f2) in the composition of the invention preferably ranges from 60:40 to 45:55. Particularly good results have been obtained at a weight ratio of fragrance formulation (f1) to fragrance formulation (f2) of around 50:50.
  • fragrance (f1) and fragrance (f2) are typically incorporated at different stages of formation of the composition of the invention.
  • the discrete polymeric microparticles (e.g. microcapsules) entrapping fragrance formulation (f2) are added in the form of a slurry to a warmed base formulation comprising other components of the composition (such as surfactants and solvents).
  • Fragrance (f1) is typically post-dosed later after the base formulation has cooled.
  • a composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability.
  • additional optional ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye.
  • foam boosting agents e.g. bactericides
  • preservatives e.g. bactericides
  • polyelectrolytes e.g. bactericides
  • anti-shrinking agents e.g. bactericides
  • anti-wrinkle agents e.g. bactericides
  • anti-oxidants e.g. bactericides
  • sunscreens e.g. bactericides
  • anti-corrosion agents e.g. ethylene glycol, colophonyl, colophonyl, colo
  • the composition comprises less than 1% alcohol and more preferably less than 0.1% alcohol.
  • ingredients used in embodiments of the invention may be obtained from so called black carbon sources or a more sustainable green source.
  • black carbon sources or a more sustainable green source.
  • the following provides a list of alternative sources for several of these ingredients and how they can be made into raw materials described herein.
  • SLES and other such alkali metal alkyl ether sulphate anionic surfactants are typically obtainable by sulphating alcohol ethoxylates. These alcohol ethoxylates are typically obtainable by ethoxylating linear alcohols.
  • primary alkyl sulphate surfactants (PAS) can be obtained from linear alcohols directly by sulphating the linear alcohol.
  • forming the linear alcohol is a central step in obtaining both PAS and alkalimetal alkyl ether sulphate surfactants.
  • linear alcohols which are suitable as an intermediate step in the manufacture of alcohol ethoxylates and therefore anionic surfactants such as sodium lauryl ether sulphate ca be obtained from many different sustainable sources. These include:
  • Primary sugars are obtained from cane sugar or sugar beet, etc., and may be fermented to form bioethanol.
  • the bioethanol is then dehydrated to form bio-ethylene which then undergoes olefin methathesis to form alkenes.
  • These alkenes are then processed into linear alcohols either by hydroformylation or oxidation.
  • An alternative process also using primary sugars to form linear alcohols can be used and where the primary sugar undergoes microbial conversion by algae to form triglycerides. These triglycerides are then hydrolysed to linear fatty acids and which are then reduced to form the linear alcohols.
  • Biomass for example forestry products, rice husks and straw to name a few may be processed into syngas by gasification. Through a Fischer Tropsch reaction these are processed into alkanes, which in turn are dehydrogenated to form olefins. These olefins may be processed in the same manner as the alkenes described above [primary sugars].
  • Waste plastic is pyrolyzed to form pyrolysed oils. This is then fractioned to form linear alkanes which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].
  • the pyrolyzed oils are cracked to form ethylene which is then processed to form the required alkenes by olefin metathesis. These are then processed into linear alcohols as described above [primary sugars].
  • MSW is turned into syngas by gasification. From syngas it may be processed as described above [primary sugars] or it may be turned into ethanol by enzymatic processes before being dehydrogenated into ethylene. The ethylene may then be turned into linear alcohols by the Ziegler Process.
  • the MSW may also be turned into pyrolysis oil by gasification and then fractioned to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.
  • the raw material can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These may be fermented to form bioethanol and then processed as described above [Primary Sugars].
  • Waste oils such as used cooking oil can be physically separated into the triglycerides which are split to form linear fatty acids and then linear alcohols as described above.
  • the used cooking oil may be subjected to the Neste Process whereby the oil is catalytically cracked to form bio-ethylene. This is then processed as described above.
  • Methane capture methods capture methane from landfill sites or from fossil fuel production.
  • the methane may be formed into syngas by gasification.
  • the syngas may be processed as described above whereby the syngas is turned into methanol ( Fischer Tropsch reaction) and then olefins before being turned into linear alcohols by hydroformylation oxidation.
  • the syngas may be turned into alkanes and then olefins by Fischer Tropsch and then dehydrogenation.
  • Carbon dioxide may be captured by any of a variety of processes which are all well known.
  • the carbon dioxide may be turned into carbon monoxide by a reverse water gas shift reaction and which in turn may be turned into syngas using hydrogen gas in an electrolytic reaction.
  • the syngas is then processed as described above and is either turned into methanol and/or alkanes before being reacted to form olefins.
  • the captured carbon dioxide is mixed with hydrogen gas before being enzymatically processed to form ethanol.
  • This is a process which has been developed by Lanzatech. From here the ethanol is turned into ethylene and then processed into olefins and then linear alcohols as described above.
  • the above processes may also be used to obtain the C16/18 chains of the C16/18 alcohol ethoxylate and/or the C16/18 ether sulfates.
  • LAS linear alkyl benzene sulphonate
  • alkenes may be produced by any of the methods described above and may be formed from primary sugars, biomass, waste plastic, MSW, carbon capture, methane capture, marine carbon to name a few.
  • the olefin is processed to form linear alcohols by hydroformylation and oxidation instead, the olefin is reacted with benzene and then sulphonate to form the LAS.
  • a method preferably a domestic method, of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the detergent composition described in the first aspect, wherein the aqueous solution contains 0.1 to 1.0g/L of the surfactants and optionally drying the textile; preferably wherein the domestic method takes place in the home using domestic appliances, wherein the method occurs at wash water temperatures of 280 to 335K.
  • Formulations are described below and the figures relate to % wt. comparative inventive LAS acid 4.6 4.6 C18AE 3.4 C12AE 3.4 LES(3EO) 3.4 3.4 NaCl 1.5 1.6 NaOH 0.6 0.6 Ethoxylate polyethylene imine polymer 2 2 Polyester soil release polymer 0.4 0.4 Sequesterant (Dequest 2066) 0.6 0.6 Preservative 0.5 0.5 Preservative 1.5 1.5 Enzymes (cellulase, protease, amylase) 0.9 0.9 Fluorescer 0.1 0.1 Fragrance 0.6 0.6 pH 6.3 6.3
  • the formulations were dosed at 50ml into a front loading automatic washing machine on a 40°C cotton cycle with 2.5kg of cotton ballast.
  • the comparative formulation gave considerably more foam, observed via the front machine portal, and led to over-foaming.
  • C18AE is Genapol O-100 (ex Clariant) an oleyl based alcohol ethoxylate with an average of 10 moles of ethoxylation.
  • Tinopal CBS-X is 4,4'-Distyryl biphenyl derivative ex BASF.
  • Enzyme weight refer to the fully formulation enzyme products received from the supplier (Celluclean ® , Evity ® (savinase) , Medley ® Novozymes ® ).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Confectionery (AREA)

Claims (14)

  1. Flüssige Waschmittelzusammensetzung, umfassend C16- und C18-Alkoholethoxylat-Tensid, wobei das C18-Alkoholethoxylat einfach ungesättigtes C18 umfasst, wobei der Anteil an einfach ungesättigtem C18 mindestens 50 Gew.-% des gesamten C16- und C18-Alkoholethoxylat-Tensids darstellt und das C16-Alkoholethoxylat mindestens 4% des gesamten C16- und C18-Alkoholethoxylat-Tensids umfasst und wobei das C16- und C18-Alkoholethoxylat durchschnittlich 8 bis 20 Ethoxylatgruppen aufweist.
  2. Zusammensetzung nach Anspruch 1, wobei der Gesamtgehalt an C16- und C18-Alkoholethoxylat 1 bis 30 Gew.-% der Zusammensetzung beträgt.
  3. Zusammensetzung nach Anspruch 1 oder 2, umfassend ein anionisches Tensid.
  4. Zusammensetzung nach Anspruch 3, wobei das anionische Tensid aus linearem Alkylbenzolsulfonat, Alkylethersalzen, primären Alkylsulfaten und MES und Mischungen davon ausgewählt ist.
  5. Zusammensetzung nach Anspruch 3 oder 4, wobei das anionische Tensid mit 1 bis 30 Gew.-% der Zusammensetzung vorliegt.
  6. Zusammensetzung nach einem vorhergehenden Anspruche, umfassend 0,1 bis 10 Gew.-% der Zusammensetzung an Reinigungspolymer, ausgewählt aus Alkoxylat-Polyethyleniminen, Polyester-Soil-Release-Polymeren, Copolymer von PEG/Vinylacetat und Mischungen davon.
  7. Zusammensetzung nach einem vorhergehenden Anspruch, umfassend Enzym.
  8. Zusammensetzung nach einem vorhergehenden Anspruch, umfassend Komplexbildner.
  9. Zusammensetzung nach einem vorhergehenden Anspruch, umfassend Benzoatsalz.
  10. Zusammensetzung nach einem vorhergehenden Anspruch, umfassend 0 bis 5 Gew.-% Fettsäure.
  11. Zusammensetzung nach einem vorhergehenden Anspruch mit einer Viskosität von 100 bis 300 mPa.s.
  12. Zusammensetzung nach einem vorhergehenden Anspruch, wobei das C16- und C18-Alkoholethoxylat-Tensid weniger als 30 Gew.-% Alkoholethoxylat mit weniger als 6 Ethoxylatgruppen umfasst.
  13. Zusammensetzung nach einem der Ansprüche 3 bis 12, wobei das anionische Tensid C16/C18-Alkylethersulfat mit durchschnittlich 3 bis 20 EO-Gruppen, vorzugsweise mit 5 bis 10, umfasst.
  14. Verfahren, vorzugsweise häusliches Verfahren, zur Behandlung eines Textils, wobei das Verfahren den Schritt umfasst: Behandeln eines Textils mit einer wässrigen Lösung von 0,5 bis 20 g/l der Waschmittelzusammensetzung, vorzugsweise einer flüssigen Waschmittelzusammensetzung, nach irgendeinem der Ansprüche 2 bis 13, wobei die wässrige Lösung vorzugsweise 0,1 bis 1,0 g/l der Tenside enthält, und optional Trocknen des Textils, wobei das häusliche Verfahren vorzugsweise im Haushalt unter Verwendung von Haushaltsgeräten durchgeführt wird, wobei das Verfahren bei Waschwassertemperaturen von 280 bis 335 K erfolgt.
EP21814812.0A 2020-12-07 2021-11-26 Zusammensetzung Active EP4256011B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20212164 2020-12-07
PCT/EP2021/083243 WO2022122426A1 (en) 2020-12-07 2021-11-26 Composition

Publications (3)

Publication Number Publication Date
EP4256011A1 EP4256011A1 (de) 2023-10-11
EP4256011B1 true EP4256011B1 (de) 2024-05-01
EP4256011C0 EP4256011C0 (de) 2024-05-01

Family

ID=73740255

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21814812.0A Active EP4256011B1 (de) 2020-12-07 2021-11-26 Zusammensetzung

Country Status (7)

Country Link
US (1) US20240124800A1 (de)
EP (1) EP4256011B1 (de)
CN (1) CN116568788A (de)
AU (1) AU2021394536A1 (de)
ES (1) ES2981321T3 (de)
WO (1) WO2022122426A1 (de)
ZA (1) ZA202305559B (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4349942A1 (de) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung
EP4349943A1 (de) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung
EP4349948A1 (de) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung
EP4349944A1 (de) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung
EP4349947A1 (de) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung
EP4349945A1 (de) * 2022-10-05 2024-04-10 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung
EP4361239A1 (de) * 2022-10-25 2024-05-01 Unilever IP Holdings B.V. Flüssigwaschmittelzusammensetzung

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
US4861512A (en) 1984-12-21 1989-08-29 The Procter & Gamble Company Sulfonated block polyesters useful as soil release agents in detergent compositions
US4956447A (en) 1989-05-19 1990-09-11 The Procter & Gamble Company Rinse-added fabric conditioning compositions containing fabric sofening agents and cationic polyester soil release polymers and preferred cationic soil release polymers therefor
WO1994020597A1 (en) 1993-03-01 1994-09-15 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
DE102005061058A1 (de) 2005-12-21 2007-07-05 Clariant Produkte (Deutschland) Gmbh Anionische Soil Release Polymere
NZ574269A (en) 2006-06-23 2012-01-12 Akzo Nobel Nv Process for preparation of alkoxylated alkylamines / alkyl ether amines with peaked distribution
US7417017B2 (en) * 2006-09-07 2008-08-26 The Dial Corporation Detergent compositions with unique builder system for enhanced stain removal
PL2192169T3 (pl) 2007-01-19 2012-10-31 Procter & Gamble Kompozycja środka piorącego zawierająca środki wybielające dla substratów celulozowych
MX311859B (es) 2009-10-23 2013-07-31 Unilever Nv Polimeros de tinte.
MX2013010375A (es) 2011-03-10 2013-10-30 Unilever Nv Polimero colorante.
WO2013142486A1 (en) 2012-03-19 2013-09-26 The Procter & Gamble Company Laundry care compositions containing dyes
US10336968B2 (en) 2014-07-09 2019-07-02 Conopco, Inc. Laundry liquid composition comprising a polyester/butyl glycol/water active blend
US10745649B2 (en) * 2017-07-07 2020-08-18 The Procter & Gamble Company Cleaning compositions comprising non-alkoxylated esteramines

Also Published As

Publication number Publication date
AU2021394536A1 (en) 2023-06-15
WO2022122426A1 (en) 2022-06-16
US20240124800A1 (en) 2024-04-18
EP4256011A1 (de) 2023-10-11
ES2981321T3 (es) 2024-10-08
CN116568788A (zh) 2023-08-08
ZA202305559B (en) 2024-09-25
EP4256011C0 (de) 2024-05-01

Similar Documents

Publication Publication Date Title
EP4256011B1 (de) Zusammensetzung
US20230365889A1 (en) Composition
WO2022228950A1 (en) Composition
EP4330366B1 (de) Zusammensetzung
EP4330363B1 (de) Zusammensetzung
EP4217455B1 (de) Zusammensetzung
EP4174156A1 (de) Zusammensetzung
EP4256012B1 (de) Zusammensetzung
EP4305140B1 (de) Zusammensetzung
EP4381036B1 (de) Zusammensetzung
WO2022122425A1 (en) Composition
WO2022248108A1 (en) A liquid laundry detergent composition comprising c16 and c18 alcohol ethoxylate surfactant and/or c16 and c18 alkyl ether sulphate
WO2023051978A1 (en) Composition
WO2023012093A1 (en) Method

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230525

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20240213

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602021012856

Country of ref document: DE

U01 Request for unitary effect filed

Effective date: 20240501

U07 Unitary effect registered

Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT SE SI

Effective date: 20240508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240901

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2981321

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20241008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240802